Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS6313083 B1
Publication typeGrant
Application numberUS 09/785,749
Publication dateNov 6, 2001
Filing dateFeb 14, 2001
Priority dateMay 16, 1995
Fee statusPaid
Also published asUS6008179, US6277807, US6288017, US6426327
Publication number09785749, 785749, US 6313083 B1, US 6313083B1, US-B1-6313083, US6313083 B1, US6313083B1
InventorsRichard M. Flynn, Dean S. Milbrath, John G. Owens, Daniel R. Vitcak, Hideto Yanome
Original Assignee3M Innovative Properties Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Azeotrope-like compositions and their use
US 6313083 B1
Abstract
The invention provides azeotrope-like compositions consisting essentially of RfOCH3, where Rf is a branched or straight chain perfluoroalkyl group having 4 carbon atoms, and one or more organic solvent(s) selected from the group consisting of: straight chain, branched chain and cyclic alkanes containing 6 to 8 carbon atoms; cyclic and acyclic ethers containing 4 to 6 carbon atoms; ketones having 3 carbon atoms; chlorinated alkanes containing 1, 3 or 4 carbon atoms; chlorinated alkenes containing 2 carbon atoms, alcohols containing 1 to 4 carbon atoms, partially fluorinated alcohols containing 2 to 3 carbon atoms, 1-bromopropane, acetonitrile, HCFC 225ca (1,1,-dichloro-2,2,3,3,3 pentafluoropropane and HCFC- 225cb (1,3-dichloro-1,1,2,2,3-pentafluoropropane).
Images(15)
Previous page
Next page
Claims(19)
We claim:
1. An azeotrope-like composition including (a) perfluorobutyl methyl ether, consisting essentially of perfluoro-n-butyl methyl ether and perfluoroisobutyl methyl ether and mixtures thereof, and (b) organic solvent, which composition is selected from the group consisting of:
(i) compositions consisting essentially of about 95 to 61 weight percent of perfluorobutyl methyl ether and about 5 to 39 weight percent cyclohexane that boil at about 54 to 56° C. at about 735 torr;
(ii) compositions consisting essentially of about 99 to 83 weight percent of perfluorobutyl methyl ether and about 1 to 17 weight percent methylcyclohexane that boil at about 58 to 60° C. at about 729 torr;
(iii) compositions consisting essentially of about 99 to 86 weight percent of perfluorobutyl methyl ether and about 1 to 14 weight percent heptane that boil at about 58 to 60° C. at about 732 torr;
(iv) compositions consisting essentially of about 99 to 88 weight percent of perfluorobutyl methyl ether and about 1 to 12 weight percent isooctane that boil at about 58 to 60° C. at about 739 torr;
(v) compositions consisting essentially of about 93 to 44 weight percent of perfluorobutyl methyl ether and about 7 to 56 weight percent hexane that boil at about 51 to 53° C. at about 736 torr.
2. A process for depositing a coating on a substrate surface comprising the step of applying to at least a portion of at least one surface of the substrate a liquid coating composition comprising:
(A) an azeotrope-like composition according to claim 1; and
(B) at least one coating material which is soluble or dispersible in the azeotrope-like composition.
3. A coating composition consisting essentially of an azeotrope-like composition according to claim 1 and a coating material.
4. A process for removing contaminants from the surface of a substrate comprising the step of contacting the substrate with one or more of the azeotrope-like compositions according to claim 1 until the contaminants are dissolved, dispersed or displaced in or by the azeotrope-like composition, and removing the azeotrope-like composition containing the dissolved, dispersed or displaced contaminants from the surface of the substrate.
5. A process according to claim 4 wherein the azeotrope-like composition further comprises a surfactant and the substrate is a fabric.
6. An azeotrope-like composition including perfluorobutyl methyl ether, wherein said ether consists essentially of about 95 weight percent perfluoro-n-butyl methyl ether, and about 5 weight percent perfluoroisobutyl methyl ether, and one organic solvent, and is selected from the group consisting of:
(i) compositions consisting essentially of the ether and cyclohexane which, when fractionally distilled, form a distillate fraction that is an azeotrope that consists essentially of about 88 weight percent of the ether and about 12 weight percent of the cyclohexane and boils at about 54° C. at about 738 torr;
(ii) compositions consisting essentially of the ether and methylcyclohexane which, when fractionally distilled, form a distillate fraction that is an azeotrope that consists essentially of about 96 weight percent of the ether and about 4 weight percent of the methylcyclohexane and boils at about 58° C. at about 734 torr;
(iii) compositions consisting essentially of the ether and heptane which, when fractionally distilled, form a distillate fraction that is an azeotrope that consists essentially of about 95 weight percent of the ether and 5 weight percent of the heptane and boils at about 57° C. at about 725 torr;
(iv) compositions consisting essentially of the ether and isooctane which, when fractionally distilled, produce a distillate fraction that is an azeotrope that consists essentially of about 96 weight percent of the ether and about 4 weight percent of the isooctane and boils at about 58° C. at about 725 torr; and
(v) compositions consisting essentially of the ether and hexane which, when fractionally distilled, produce a distillate fraction that is an azeotrope that consists essentially of about 79 weight percent of the ether and about 21 weight percent of the isooctane and boils at about 51° C. at about 730 torr.
7. An azeotrope-like composition according to claim 6 wherein the concentrations of the ether and the organic solvent in the azeotrope-like composition differ from the concentrations of such components in the corresponding azeotrope by no more than five percent.
8. An azeotrope-like composition according to claim 6 wherein the azeotrope-like composition is an azeotrope.
9. A process for depositing a coating on a substrate surface comprising the step of applying to at least a portion of at least one surface of the substrate a liquid coating composition comprising:
(A) an azeotrope-like composition according to claim 6; and
(B) at least one coating material which is soluble or dispersible in the azeotrope-like composition.
10. A coating composition consisting essentially of an azeotrope-like composition according to claim 6 and a coating material.
11. A process for removing contaminants from the surface of a substrate comprising the step of contacting the substrate with one or more of the azeotrope-like compositions according to claim 6 until the contaminants are dissolved, dispersed or displaced in or by the azeotrope-like composition, and removing the azeotrope-like composition containing the dissolved, dispersed or displaced contaminants from the surface of the substrate.
12. A process according to claim 11 wherein the azeotrope-like composition further comprises a surfactant and the substrate is a fabric.
13. An azeotrope-like composition including perfluorobutyl methyl ether, wherein said ether consists essentially of about 35 weight percent perfluoro-n-butyl methyl ether, and about 65 weight percent perfluoroisobutyl methyl ether, and one organic solvent, and is selected from the group consisting of:
(i) compositions consisting essentially of the ether and methylcyclohexane, the compositions ,when fractionally distilled, form a distillate fraction that is an azeotrope that consists essentially of about 97 weight percent of the ether and about 3 weight percent of the methylcyclohexane and boils at about 59° C. at about 738 torr;
(ii) compositions consisting essentially of the ether and heptane, the compositions, when fractionally distilled, form a distillate fraction that is an azeotrope that consists essentially of about 94 weight percent of the ether and 6 weight percent of the heptane and boils at about 59° C. at about 730 torr; and
(iii) compositions consisting essentially of the ether and isooctane, the compositions, when fractionally distilled, produce a distillate fraction that is an azeotrope that consists essentially of about 96 weight percent of the ether and about 4 weight percent of the isooctane and boils at about 58° C. at about 731 torr.
14. An azeotrope-like composition according to claim 13 wherein the concentrations of the ether and the organic solvent in the azeotrope-like composition differ from the concentrations of such components in the corresponding azeotrope by no more than five percent.
15. An azeotrope-like composition according to claim 13 wherein the azeotrope-like composition is an azeotrope.
16. A process for depositing a coating on a substrate surface comprising the step of applying to at least a portion of at least one surface of the substrate a liquid coating composition comprising:
(A) an azeotrope-like composition according to claim 13; and
(B) at least one coating material which is soluble or dispersible in the azeotrope-like composition.
17. A coating composition consisting essentially of an azeotrope-like composition according to claim 13 and a coating material.
18. A process for removing contaminants from the surface of a substrate comprising the step of contacting the substrate with one or more of the azeotrope-like compositions according to claim 13 until the contaminants are dissolved, dispersed or displaced in or by the azeotrope-like composition, and removing the azeotrope-like composition containing the dissolved, dispersed or displaced contaminants from the surface of the substrate.
19. A process according to claim 18 wherein the azeotrope-like composition further comprises a surfactant and the substrate is a fabric.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. patent application Ser. No. 09/429,186, filed Oct. 28, 1999 allowed; which was a division of U.S. patent application Ser. No. 09/157,465, filed on Sep. 21, 1998 U.S. Pat. No. 6,008,179; which was a division of U.S. patent application Ser. No. 08/648,264, filed on May 15, 1996 U.S. Pat No. 5,827,812; which was a continuation-in-part of U.S. patent application Ser. No. 08/604,002, filed on Feb. 20, 1996, now abandoned; which is a continuation-in-part of U.S. patent application Ser. No. 08/441,960, filed on May 16, 1995, now abandoned.

FIELD OF THE INVENTION

The invention relates to azeotropes and methods of using azeotropes to clean substrates, deposit coatings and transfer thermal energy.

BACKGROUND

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been used in a wide variety of solvent applications such as drying, cleaning (e.g., the removal of flux residues from printed circuit boards), and vapor degreasing. Such materials have also been used in refrigeration and heat transfer processes. While these materials were initially believed to be environmentally-benign, they have now been linked to ozone depletion. According to the Montreal Protocol and its attendant amendments, production and use of CFCs must be discontinued (see, e.g., P. S. Zurer, “Looming Ban on Production of CFCs, Halons Spurs Switch to Substitutes,” Chemical & Engineering News, page 12, Nov. 15, 1993). The characteristics sought in replacements, in addition to low ozone depletion potential, typically have included boiling point ranges suitable for a variety of solvent cleaning applications, low flammability, and low toxicity. Solvent replacements also should have the ability to dissolve both hydrocarbon-based and fluorocarbon-based soils. Preferably, substitutes will also be low in toxicity, have no flash points (as measured by ASTM D3278-89), have acceptable stability for use in cleaning applications, and have short atmospheric lifetimes and low global warming potentials.

Certain perfluorinated (PFCs) and highly fluorinated hydrofluorocarbon (HFCs) materials have also been evaluated as CFC and HCFC replacements in solvent applications. While these compounds are generally sufficiently chemically stable, nontoxic and nonflammable to be used in solvent applications, PFCs tend to persist in the atmosphere, and PFCs and HFCs are generally less effective than CFCs and HCFCs for dissolving or dispersing hydrocarbon materials. Also, mixtures of PFCs or HFCs with hydrocarbons tend to be better solvents and dispersants for hydrocarbons than PFCs or HFCs alone.

Many azeotropes possess properties that make them useful solvents. For example, azeotropes have a constant boiling point, which avoids boiling temperature drift during processing and use. In addition, when a volume of an azeotrope is used as a solvent, the properties of the solvent remain constant because the composition of the solvent does not change. Azeotropes that are used as solvents also can be recovered conveniently by distillation.

There currently is a need for azeotrope or azeotrope-like compositions that can replace CFC- and HCFC-containing solvents. Preferably these compositions would be non-flammable, have good solvent power, cause no damage to the ozone layer and have a relatively short atmospheric lifetime so that they do not significantly contribute to global warming.

SUMMARY OF THE INVENTION

In one aspect, the invention provides azeotrope-like compositions consisting essentially of hydrofluorocarbon ether and one or more organic solvents. The hydrofluorocarbon ether is represented by the general formula RfOCH3, where Rf is a branched or straight chain perfluoroalkyl group having 4 carbon atoms, and the ether may be a single compound or a mixture of the branched and straight chain ether compounds. The organic solvents are selected from the group consisting of: straight chain, branched chain and cyclic alkanes containing 6 to 8 carbon atoms; cyclic and acyclic ethers containing 4 to 6 carbon atoms; ketones having 3 carbon atoms; chlorinated alkanes containing 1, 3 or 4 carbon atoms; chlorinated alkenes containing 2 to 3 carbon atoms, alcohols containing 1 to 4 carbon atoms, partially fluorinated alcohols containing 2 to 3 carbon atoms, 1-bromopropane, acetonitrile, HCFC-225ca (1,1,-dichloro-2,2,3,3,3 pentafluoropropane) and HCFC -225cb (1,3-dichloro-1,1,2,2,3-pentafluoropropane). While the concentrations of the hydrofluorocarbon ether and organic solvent included in an azeotrope-like composition may vary somewhat from the concentrations found in the azeotrope formed between them and remain a composition within the scope of this invention, the boiling points of the azeotrope-like compositions will be substantially the same as those of their corresponding azeotropes. Preferably, the azeotrope-like compositions boil, at ambient pressure, at temperatures that are within about 1° C. of the temperatures at which their corresponding azeotropes boil at the same pressure.

In another aspect, the invention provides a method of cleaning objects by contacting the object to be cleaned with one or more of the azeotrope-like compositions of this invention or the vapor of such compositions until undesirable contaminants or soils on the object are dissolved, dispersed or displaced and rinsed away.

In yet another aspect, the invention also provides a method of coating substrates using the azeotrope-like compositions as solvents or carriers for the coating material. The process comprises the step of applying to at least a portion of at least one surface of a substrate a liquid coating composition comprising: (a) an azeotrope-like composition, and (b) at least one coating material which is soluble or dispersible in the azeotrope-like composition. Preferably, the process further comprises the step of removing the azeotrope-like composition from the liquid coating composition, for example, by evaporation.

The invention also provides coating compositions consisting essentially of an azeotrope-like composition and a coating material which are useful in the aforementioned coating process.

In yet another aspect, the invention provides a method of transferring thermal energy using the azeotrope-like compositions of this invention as heat transfer fluids (e.g. primary or secondary heat transfer media).

DETAILED DESCRIPTION

The azeotrope-like compositions are mixtures of hydrofluorocarbon ether and one or more organic solvents which, if fractionally distilled, produce a distillate fraction that is an azeotrope of the hydrofluorocarbon ether and organic solvent(s).

The azeotrope-like compositions boil at temperatures that are essentially the same as the boiling points of their corresponding azeotropes. Preferably, the boiling point of an azeotrope-like composition at ambient pressure is within about 1° C. of the boiling point of its corresponding azeotrope measured at the same pressure. More preferably, the azeotrope-like compositions will boil at temperatures that are within about 0.5° C. of the boiling points of their corresponding azeotropes measured at the same pressure.

The concentrations of the hydrofluorocarbon ether and organic solvent or organic solvents in a particular azeotrope-like composition may vary substantially from the amounts contained in the composition's corresponding azeotrope, and the magnitude of such permissible variation depends upon the organic solvent or solvents used to make the azeotrope-like composition. Preferably, the concentrations of hydrofluorocarbon ether and organic solvent in an azeotrope-like composition vary no more than about ten percent from the concentrations of such components contained in the azeotrope formed between them at ambient pressure. More preferably, the concentrations are within about five percent of those contained in the azeotrope. Most preferably, the azeotrope-like composition contains essentially the same concentrations of the ether and solvent as are contained in the azeotrope formed between them at ambient pressure. Where the concentrations of ether and organic solvent in an azeotrope-like composition differ from the concentrations contained in the corresponding azeotrope, the preferred compositions contain a concentration of the ether that is in excess of the ether's concentration in the azeotrope. Such compositions are likely to be less flammable than azeotrope-like compositions in which the organic solvent is present in a concentration that is in excess of its concentration in the azeotrope. The most preferred azeotrope-like compositions will exhibit no significant change in the solvent power of the compositions over time.

The azeotrope-like compositions of this invention may also contain, in addition to the hydrofluorocarbon ether and organic solvent, small amounts of other compounds which do not interfere in the formation of the azeotrope. For example, small amounts of surfactants may be present in the azeotrope-like compositions of the invention to improve the dispersibility or solubility of materials, such as water, soils or coating materials (e.g., perfluoropolyether lubricants and fluoropolymers), in the azeotrope-like composition. Azeotropes or azeotrope-like compositions containing as a component 1,2-trans-dichloroethylene preferably also contain about 0.25 to 1 weight percent of nitromethane and about 0.05 to 0.4 weight percent of epoxy butane to prevent degradation of the 1,2-trans-dichloroethylene. Most preferably, such compositions will contain about 0.5 weight percent nitromethane and 0.1 weight percent of the epoxy butane.

The characteristics of azeotropes are discussed in detail in Merchant, U.S. Pat. No. 5,064,560 (see, in particular, col. 4, lines 7-48).

The hydrofluorocarbon ether useful in the invention can be represented by the following general formula:

Rf—O—CH3  (I)

where, in the above formula, Rf is selected from the group consisting of linear or branched perfluoroalkyl groups having 4 carbon atoms. The ether may be a mixture of ethers having linear or branched perfluoroalkyl Rf groups. For example, perfluorobutyl methyl ether containing about 95 weight percent perfluoro-n-butyl methyl ether and 5 weight percent perfluoroisobutyl methyl ether and perfluorobutyl methyl ether containing about 60 to 80 weight percent perfluoroisobutyl methyl ether and 40 to 20 weight percent perfluoro-n-butyl methyl ether are useful in this invention.

The hydrofluorocarbon ether can be prepared by alkylation of:

CF3CF2CF2CF2O, CF3CF(CF3)CF2O, C2F5C(CF3)FO, C(CF3)3O and mixtures thereof. The first three aforementioned perfluoroalkoxides can be prepared by reaction of: CF3CF2CF2C(O)F, CF3CF(CF3)C(O)F, and C2F5C(O)CF3 and mixtures thereof, with any suitable source of anhydrous fluoride ion such as anhydrous alkali metal fluoride (e.g., potassium fluoride or cesium fluoride) or anhydrous silver fluoride in an anhydrous polar, aprotic solvent in the presence of a quaternary ammonium compound such as “ADOGEN 464” available from the Aldrich Chemical Company. The perfluoroalkoxide, C(CF3)3O, can be prepared by reacting C(CF3)3OH with a base such as KOH in an anhydrous polar, aprotic solvent in the presence of a quaternary ammonium compound. General preparative methods for the ethers are also described in French Patent No. 2,287,432 and German Patent No. 1,294,949.

Suitable alkylating agents for use in the preparation include dialkyl sulfates (e.g., dimethyl sulfate), alkyl halides (e.g., methyl iodide), alkyl p-toluenesulfonates (e.g., methyl p-toluenesulfonate), alkyl perfluoroalkanesulfonates (e.g., methyl perfluoromethanesulfonate), and the like. Suitable polar, aprotic solvents include acyclic ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; carboxylic acid esters such as methyl formate, ethyl formate, methyl acetate, diethyl carbonate, propylene carbonate, and ethylene carbonate; alkyl nitriles such as acetonitrile; alkyl amides such as N,N-dimethylformamide, N,N-diethylformamide, and N-methylpyrrolidone; alkyl sulfoxides such as dimethyl sulfoxide; alkyl sulfones such as dimethylsulfone, tetramethylene sulfone, and other sulfolanes; oxazolidones such as N-methyl-2-oxazolidone; and mixtures thereof.

Perfluorinated acyl fluorides (for use in preparing the hydrofluorocarbon ether) can be prepared by electrochemical fluorination (ECF) of the corresponding hydrocarbon carboxylic acid (or a derivative thereof), using either anhydrous hydrogen fluoride (Simons ECF) or KF.2HF (Phillips ECF) as the electrolyte. Perfluorinated acyl fluorides and perfluorinated ketones can also be prepared by dissociation of perfluorinated carboxylic acid esters (which can be prepared from the corresponding hydrocarbon or partially-fluorinated carboxylic acid esters by direct fluorination with fluorine gas). Dissociation can be achieved by contacting the perfluorinated ester with a source of fluoride ion under reacting conditions (see the methods described in U.S. Pat. No. 3,900,372 (Childs) and U.S. Pat. No. 5,466,877 (Moore), the description of which is incorporated herein by reference) or by combining the ester with at least one initiating reagent selected from the group consisting of gaseous, non-hydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one non-hydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acylating agents.

Initiating reagents which can be employed in the dissociation are those gaseous or liquid, non-hydroxylic nucleophiles and mixtures of gaseous, liquid, or solid, non-hydroxylic nucleophile(s) and solvent (hereinafter termed “solvent mixtures”) which are capable of nucleophilic reaction with perfluorinated esters. The presence of small amounts of hydroxylic nucleophiles can be tolerated. Suitable gaseous or liquid, non-hydroxylic nucleophiles include dialkylamines, trialkylamines, carboxamides, alkyl sulfoxides, amine oxides, oxazolidones, pyridines, and the like, and mixtures thereof. Suitable non-hydroxylic nucleophiles for use in solvent mixtures include such gaseous or liquid, non-hydroxylic nucleophiles, as well as solid, non-hydroxylic nucleophiles, e.g., fluoride, cyanide, cyanate, iodide, chloride, bromide, acetate, mercaptide, alkoxide, thiocyanate, azide, trimethylsilyl difluoride, bisulfite, and bifluoride anions, which can be utilized in the form of alkali metal, ammonium, alkyl-substituted ammonium (mono-, di-, tri-, or tetra-substituted), or quaternary phosphonium salts, and mixtures thereof. Such salts are in general commercially available but, if desired, can be prepared by known methods, e.g., those described by M. C. Sneed and R. C. Brasted in Comprehensive Inorganic Chemistry, Volume Six (The Alkali Metals), pages 61-64, D. Van Nostrand Company, Inc., New York (1957), and by H. Kobler et al. in Justus Liebigs Ann. Chem., 1978, 1937. 1,4-diazabicyclo[2.2.2]octane and the like are also suitable solid nucleophiles.

The hydrofluorocarbon ethers used to prepare the azeotrope-like compositions of this invention do not deplete the ozone in the earth's atmosphere and have surprisingly short atmospheric lifetimes thereby minimizing their impact on global warming. Reported in Table 1 is an atmospheric lifetime for the hydrofluorocarbon ether which was calculated using the technique described in Y. Tang, Atmospheric Fate of Various Fluorocarbons, M.S. Thesis, Massachusetts Institute of Technology (1993). The results of this calculation are presented under the heading “Atmospheric Lifetime (years)”. The atmospheric lifetimes of the hydrofluorocarbon ether and its corresponding hydrofluorocarbon alkane were also calculated using a correlation developed between the highest occupied molecular orbital energy and the known atmospheric lifetimes of hydrofluorocarbons and hydrofluorocarbon ethers that is similar to a correlation described by Cooper et al. in Atmos. Environ. 26A, 7, 1331 (1992). These values are reported in Table 1 under the heading “Estimated Atmospheric Lifetime.” The global warming potential of the hydrofluorocarbon ether was calculated using the equation described in the Intergovernmental Panel's Climate Change: The IPCC Scientific Assessment, Cambridge University Press (1994). The results of that calculation are presented in Table 1 under the heading “Global Warming Potential”. It is apparent from the data in Table 1 that the hydrofluorocarbon ether has a relatively short estimated atmospheric lifetime and relatively small global warming potential. Surprisingly, the hydrofluorocarbon ether also has a significantly shorter estimated atmospheric lifetime than its corresponding hydrofluorocarbon alkane.

TABLE 1
Estimated
Atmospheric Atmospheric Global Warming
Lifetime Lifetime Potential
Compound (years) (years) (100 year ITH)
C4F9—CH3 7.0
C4F9—O—CH3 1.9 4.1 500

Typical organic solvents useful in this invention include straight chain, branched chain and cyclic alkanes containing 6 to 8 carbon atoms (e.g., cyclohexane, methylcyclohexane, hexane, heptane and isooctane); cyclic or acyclic ethers containing 4 to 6 carbon atoms (e.g., t-butyl methyl ether, tetrahydrofuran and di-isopropyl ether); ketones containing 3 carbon atoms (e.g., acetone), chlorinated alkanes containing one, three or four carbon atoms (e.g., methylene chloride, 1,2-dichloropropane, 2,2-dichloropropane, t-butyl chloride, i-butyl chloride, 2-chlorobutane and 1-chlorobutane); chlorinated alkenes containing 2 to 3 carbon atoms (e.g., cis-1,2-dichloroethylene, 1,1,2-trichloroethylene, trans-1,2-dichloroethylene and 2,3-dichloro-1-propene); alcohols containing 1 to 4 carbon atoms (e.g., methanol, ethanol, 1-propanol, 2-propanol, i-butanol, t-butanol, 2-butanol), fluorinated alcohols having 2 to 3 carbon atoms (e.g., trifluoroethanol, pentafluoropropanol and hexafluoro-2-propanol), 1 -bromopropane, acetonitrile and a 55 wt %/45 wt % mixture of HCFC-225ca and HCFC-225cb (respectively).

One or more of the organic solvents can be mixed with perfluorobutyl methyl ether to prepare the azeotropes and azeotrope-like compositions. Various examples of such azeotropes and azeotrope-like compositions are described in the Examples.

When nonhalogenated alcohols having 1 to 3 carbon atoms (i.e., methanol, ethanol, 1-propanol and isopropanol) are combined with the ether to make an azeotrope or azeotrope-like composition, the isomer composition of the ether may have some effect on the composition of the azeotrope. However, even in such mixtures, the boiling point of the azeotropes formed between the components are essentially the same.

Preferably, the azeotrope-like compositions are homogeneous. That is, they form a single phase under ambient conditions, i.e., at room temperature and atmospheric pressure.

The azeotrope-like compositions are prepared by mixing the desired amounts of hydrofluorocarbon ether, organic solvent or solvents and any other minor components such as surfactants together using conventional mixing means.

The cleaning process of the invention can be carried out by contacting a contaminated substrate with one of the azeotrope-like compositions of this invention until the contaminants on the substrate are dissolved, dispersed or displaced in or by the azeotrope-like composition and then removing (for example by rinsing the substrate with fresh, uncontaminated azeotrope-like composition or by removing a substrate immersed in an azeotrope-like composition from the bath and permitting the contaminated azeotrope-like composition to flow off of the substrate) the azeotrope-like composition containing the dissolved, dispersed or displaced contaminant from the substrate. The azeotrope-like composition can be used in either the vapor or the liquid state (or both), and any of the known techniques for “contacting” a substrate can be utilized. For example, the liquid azeotrope-like composition can be sprayed or brushed onto the substrate, the vaporous azeotrope-like composition can be blown across the substrate, or the substrate can be immersed in either a vaporous or a liquid azeotrope-like composition. Elevated temperatures, ultrasonic energy, and/or agitation can be used to facilitate the cleaning. Various different solvent cleaning techniques are described by B. N. Ellis in Cleaning and Contamination of Electronics Components and Assemblies, Electrochemical Publications Limited, Ayr, Scotland, pages 182-94 (1986).

Both organic and inorganic substrates can be cleaned by the process of the invention. Representative examples of the substrates include metals; ceramics; glass; polymers such as: polycarbonate, polystyrene and acrylonitrile-butadiene-styrene copolymer; natural fibers (and fabrics derived therefrom) such as: cotton, silk, linen, wool, ramie; fur; leather and suede; synthetic fibers (and fabrics derived therefrom) such as: polyester, rayon, acrylics, nylon, polyolefin, acetates, triacetates and blends thereof; fabrics comprising a blend of natural and synthetic fibers; and composites of the foregoing materials. The process is especially useful in the precision cleaning of electronic components (e.g., circuit boards), optical or magnetic media, and medical devices and medical articles such as syringes, surgical equipment, implantable devices and prostheses.

The cleaning process of the invention can be used to dissolve or remove most contaminants from the surface of a substrate. For example, materials such as light hydrocarbon contaminants; higher molecular weight hydrocarbon contaminants such as mineral oils, greases, cutting and stamping oils and waxes; fluorocarbon contaminants such as perfluoropolyethers, bromotrifluoroethylene oligomers (gyroscope fluids), and chlorotrifluoroethylene oligomers (hydraulic fluids, lubricants); silicone oils and greases; solder fluxes; particulates; and other contaminants encountered in precision, electronic, metal, and medical device cleaning can be removed. The process is particularly useful for the removal of hydrocarbon contaminants (especially, light hydrocarbon oils), fluorocarbon contaminants, particulates, and water (as described in the next paragraph).

To displace or remove water from substrate surfaces, the cleaning process of the invention can be carried out as described in U.S. Pat. No. 5,125,978 (Flynn et al.) by contacting the surface of an article with an azeotrope-like composition which preferably contains a non-ionic fluoroaliphatic surface active agent. The wet article is immersed in the liquid azeotrope-like composition and agitated therein, the displaced water is separated from the azeotrope-like composition, and the resulting water-free article is removed from the liquid azeotrope-like composition. Further description of the process and the articles which can be treated are found in said U.S. Pat. No. 5,125,978 and the process can also be carried out as described in U.S. Pat. No. 3,903,012 (Brandreth).

The azeotrope-like compositions can also be used in coating deposition applications, where the azeotrope-like composition functions as a carrier for a coating material to enable deposition of the material on the surface of a substrate. The invention thus also provides a coating composition comprising the azeotrope-like composition and a process for depositing a coating on a substrate surface using the azeotrope-like composition. The process comprises the step of applying to at least a portion of at least one surface of a substrate a coating of a liquid coating composition comprising (a) an azeotrope-like composition, and (b) at least one coating material which is soluble or dispersible in the azeotrope-like composition. The coating composition can further comprise one or more additives (e.g., surfactants, coloring agents, stabilizers, anti-oxidants, flame retardants, and the like). Preferably, the process further comprises the step of removing the azeotrope-like composition from the deposited coating by, e.g., allowing evaporation (which can be aided by the application of, e.g., heat or vacuum).

The coating materials which can be deposited by the process include pigments, lubricants, stabilizers, adhesives, anti-oxidants, dyes, polymers, pharmaceuticals, release agents, inorganic oxides, and the like, and combinations thereof Preferred materials include perfluoropolyether, hydrocarbon, and silicone lubricants; amorphous copolymers of tetrafluoroethylene; polytetrafluoroethylene; and combinations thereof. Representative examples of materials suitable for use in the process include titanium dioxide, iron oxides, magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid, acrylic adhesives, polytetrafluoroethylene, amorphous copolymers of tetrafluoroethylene, and combinations thereof. Any of the substrates described above (for cleaning applications) can be coated via the process of the invention. The process can be particularly useful for coating magnetic hard disks or electrical connectors with perfluoropolyether lubricants or medical devices with silicone lubricants.

To form a coating composition, the components of the composition (i.e., the azeotrope-like composition, the coating material(s), and any additive(s) utilized) can be combined by any conventional mixing technique used for dissolving, dispersing, or emulsifying coating materials, e.g., by mechanical agitation, ultrasonic agitation, manual agitation, and the like. The azeotrope-like composition and the coating material(s) can be combined in any ratio depending upon the desired thickness of the coating, but the coating material(s) preferably constitute from about 0.1 to about 10 weight percent of the coating composition for most coating applications.

The deposition process of the invention can be carried out by applying the coating composition to a substrate by any conventional technique. For example, the composition can be brushed or sprayed (e.g., as an aerosol) onto the substrate, or the substrate can be spin-coated. Preferably, the substrate is coated by immersion in the composition. Immersion can be carried out at any suitable temperature and can be maintained for any convenient length of time. If the substrate is a tubing, such as a catheter, and it is desired to ensure that the composition coats the lumen wall, it may be advantageous to draw the composition into the lumen by the application of reduced pressure.

After a coating is applied to a substrate, the azeotrope-like composition can be removed from the deposited coating by evaporation. If desired, the rate of evaporation can be accelerated by application of reduced pressure or mild heat. The coating can be of any convenient thickness, and, in practice, the thickness will be determined by such factors as the viscosity of the coating material, the temperature at which the coating is applied, and the rate of withdrawal (if immersion is utilized).

Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. Unless otherwise stated all amounts are in grams and all percentages are weight percentages.

EXAMPLES Examples 1-2

The preparation of the perfluorobutyl methyl ether used to make the azeotrope-like compositions described in later Examples is described below.

Preparation of Ether “A”. “Ether A”, used to prepare some of the azeotrope-like compositions of the following Examples, was prepared as follows.

Perfluoro-n-butyryl fluoride, a reactant used to make Ether A, was prepared by electrochemically fluorinating n-butyryl chloride (>99% pure) in a Simons ECF cell of the type described in U.S. Pat. No. 2,713,593 (Brice et al. ) and in Preparation, Properties and Industrial Applications of Organofluorine Compounds, R. E. Banks, ed., John Wiley and sons, New York, 1982, pp. 19 to 43.

The gaseous products from the Simons cell were cooled to −62° C. (−80° F.) and the resulting phases separated. The upper HF phase was recycled back to the ECF cell and the lower product phase collected.

The product phase yielded a mixture of approximately greater than 73.5% perfluoro-n-butyryl fluoride, 3.5% perfluoro-isobutyryl fluoride and 23% perfluorinated, inert cyclic compounds. This product phase was used in subsequent alkylations without further purification.

Into a 20 gallon Hastalloy C reactor with a stirrer and a cooling system was charged 6 kg (103.1 mole) of spray-dried potassium fluoride. The reactor was sealed and the pressure inside the reactor was reduced to less than 100 torr. Anhydrous dimethyl formamide (25.1 kg) was then added to the reactor and the reactor was cooled to below 0° C. with constant agitation. The perfluorobutyryl fluoride product described above (25.1 kg, 67.3 mole) was added to the reactor contents. When the temperature of the reactor reached −20° C., dimethyl sulfate (12.0 kg, 95.1 mole) was added to the reactor over a period of approximately two hours. The resulting mixture was then held for 16 hours with continued agitation, was raised to 50° C. for an additional four hours to facilitate complete reaction, and was cooled to 20° C. Then, volatile material (primarily perfluorooxacyclopentane present in the starting perfluorofluorobutyryl fluoride) was vented from the reactor over a three-hour period. The reactor was then resealed, and water (6.0 kg) was added slowly to the reactor. After the exothermic reaction of the water with unreacted perfluorobutyryl fluoride subsided, the reactor was cooled to 25° C., and the reactor contents were stirred for 30 minutes. The reactor pressure was carefully vented, and the lower organic phase of the resulting product was removed to afford 22.6 kg of product. The crude product was treated with 68% aqueous KOH at 60° C. overnight, water was added and the product azeotropically distilled. The resulting distillate was phase-separated and the product phase fractionally distilled through a 2 foot (61 cm) Oldershaw column. Analysis revealed the product to be approximately 95 wt % perfluoro-n-butyl methyl ether and 5 wt. % perfluoro-isobutyl methyl ether and the product boiled at 59° C. (at 734.3 torr). The product identity was confirmed by GCMS, 1H and 19F NMR and IR.

Preparation of Ether “B”. Perfluoroisobutyryl fluoride, a reactant that was used to make Ether B, was prepared by fluorinating isobutyric anhydride (>99% pure), in a Simons ECF cell (as described above) to form a perfluorobutyryl fluoride product containing approximately 56 wt. % perfluoroisobutyryl fluoride, 24 wt. % perfluoro-n-butyryl fluoride and 20 wt. % percent perfluorinated, inert products.

Ether B was then prepared by charging into a 100 gallon hastelloy reactor: spray-dried potassium fluoride (48 pounds, 375 moles), anhydrous diglyme (307 pounds), Adogenm™ 464 (3.4 pounds, 3.2 moles), triethylamine (12 pounds, 53.9 moles) and perfluorobutyryl fluoride product (190 pounds, 319 moles, supra). While stirring at 75° F., dimethyl sulfate (113 pounds, 407 moles) was pumped into the reactor. The reactor was held at 104° F. for approximately two hours then heated to 140° F. and allowed to react overnight.

The reactor was then charged to 20 wt % aqueous potassium hydroxide (123 pounds) to neutralize any unreacted dimethyl sulfate and stirred for 30 minutes at 70° F. at a solution pH greater than 13. Aqueous HF was added to the solution until the pH was 7 to 8, and the product perfluorobutyl methyl ether fraction was distilled from the reaction mixture. The distillate was washed with water to remove methanol, then fractionally distilled to further purify the desired product. The process provided a product that was approximately 65% perfluoro-isobutyl methyl ether and 35% perfluoro-n-butyl methyl ether and boiled at about 59° C. at 734.2 torr. The product identity was confirmed by GCMS, 1H and 19F NMR and IR.

Examples 3-48 Preparation and Identification of Azeotrope Compositions: Ebulliometer Method

The azeotropes of this invention were initially identified by screening mixtures of hydrofluorocarbon ether and various organic solvents using an ebulliometer or boiling point apparatus (specifically a Model MBP-100 available from Cal-Glass for Research, Inc., Costa Mesa, Calif.). The lower boiling component of the test mixtures (typically an amount of 25 to 30 mLs) was added to the boiling point apparatus, heated and allowed to equilibrate to its boiling point (typically about 30 minutes). After equilibration, the boiling point was recorded , a 1.0 mL aliquot of the higher boiling component was added to the apparatus and the resulting mixture was allowed to equilibrate for about 30 minutes at which time the boiling point was recorded. The test continued basically as described above, with additions to the test mixture of 1.0 mL of the higher boiling point component every 30 minutes until 15 to 20 mLs of the higher boiling point component had been added. The presence of an azeotrope was noted when the test mixture exhibited a lower boiling point than the boiling point of the lowest boiling component of the test mixture. The compositions corresponding to the aforementioned boiling points were determined. The composition (volume %) of the organic solvent in the composition was then plotted as a function of boiling point. The azeotrope-like compositions boiling at temperatures within about 1° C. of the respective azeotrope boiling point were then identified from the plot and this compositional data (on a weight % basis) as well as the boiling point range corresponding to the compositions (expressed as the difference between the composition boiling point and the azeotrope boiling point) are presented in Table 2.

The organic solvents used to prepare the azeotrope-like compositions described in these Examples were purchased commercially from the Aldrich Chemical Company and the Fluka Chemical Company, except for HCFC-225 calcb which was purchased from Asahi Glass Company as AK-225 ( a mixture of 45 weight percent HCFC-225ca, i.e., C2F5CHCl2, and 55 weight percent of HCFC-225cb, i.e., CF2ClCF2CHClF)

TABLE 2
Conc. Solvent Conc. Ether Boiling Point
Ex. Organic Solvent (wt %) (wt %) (° C.) Pressure (torr)
3 Cyclohexane: Ether A 4.9-38.8 95.1-61.2 55.0 735.2
4 Cyclohexane: Ether B 4.9-38.8 95.1-61.2
5 Methylcyclohexane: Ether A 1.0-16.6  99-83.4 58.6 728.6
6 Methylcyclohexane: Ether B 1.0-16.6 99.0-83.4
7 Hexane: Ether A 7.3-55.6 92.7-44.4 52.1 735.8
8 Heptane: Ether A 1.0-14.4 98.6-85.6 58.7 732.3
9 Heptane: Ether B 1.0-14.4 98.6-85.6
10 Isooctane: Ether A 0.9-11.5 99.1-88.5 58.9 738.5
11 Isooctane: Ether B 0.9-11.5 99.1-88.5
12 Diisopropyl ether: Ether A 3.0-34.4 97.0-65.6 57.0 736.5
13 Methyl t-butyl ether: Ether A 21.0-78.3  79.0-21.7 51.2 723.2
14 Tetrahydrofuran: Ether A 7.5-58   92.5-42.0 55.3 725.4
15 Acetone: Ether A 13.6-66.5  86.4-33.5 50.3 728.5
16 trans-1,2-Dichloroethylene: 24.6-83.8  75.4-16.2 40.7 727.5
Ether A
17 trans-1,2-Dichloroethylene: 24.6-82.6  75.4-17.4 40.3 729.3
Ether B
18 cis-1,2-Dichloroethylene: 28.0*-70.8  72.0-29.2 52.2 741.0
Ether B
19 1,1,2-Trichloroethylene: 2.0-31.5 98.0-68.5 57.8 736.5
Ether B
20 1-Chlorobutane: Ether A 3.0-31.7 97.0-68.3 57.0 728.4
21 1-Chlorobutane: Ether B 3.0-31.7 97.0-68.3
22 2-Chlorobutane: Ether B 6.7-44.6 93.3-55.4 55.0 736.9
23 i-Butyl chloride: Ether B 6.1-38   93.9-62.0 54.6 730.3
24 t-Butyl chloride: Ether A 28.3-86.7  71.7-13.3 47.0 732.8
25 t-Butyl chloride: Ether B 28.3-86.7  71.7-13.3
26 1,2-Dichloropropane: Ether A 1.5-17.9 98.5-82.1 58.9 724.1
27 1,2-Dichloropropane: Ether B 1.5-17.9 98.5-82.1
28 2,2-Dichloropropane: Ether A 8.2-42.9 91.8-57.1 55.9 734.6
29 2,2-Dichloropropane: Ether B 8.2-42.9 91.8-57.l
30 Methylene chloride: Ether B 17.5-92.1  82.5-7.9  34.5 736.6
31 Methanol: Ether A 3.3-48.4 96.7-51.6 13
32 Methanol: Ether B 3.3-48.4 96.7-51.6 45.8 732.8
33 Ethanol: Ether A 2.7-30.0 97.3-70.0
34 Ethanol: Ether B 2.7-30.0 97.3-70.0 51.8 727.6
35 2-Propanol: Ether A 1.6-39.0 98.4-61.0
36 2-Propanol: Ether B 1.6-39.0 98.4-61.0 54.4 724.9
37 1-Propanol: Ether A 1.9-34.0 98.1-66.0
38 1-Propanol: Ether B 1.9-34.0 98.1-66.0 56.6 732.7
39 2-Butanol: Ether B 1.1-24.8 98.9-75.2 58.3 742.3
40 i-Butanol: Ether B 1.1-27.7 98.9-72.3 58.1 729.5
41 t-Butanol: Ether B 1.6-22.1 98.4-77.9 56.4 739.4
42 Trifluoroethanol: Ether B 5.5-40.8 94.5-59.2 52.1 721.6
43 Pentafluoropropanol: Ether B 5.0-42.1 95.0-57.9 56.8 731.5
43a Hexafluoro-2-propanol: Ether 15.7-68.5  84.3-31.5 52.1 729.1
B
44 1-Bromopropane: Ether B 11.0-50.4  89.0-49.6 53.3 728.9
45 Acetonitrile: Ether A 2.1-22.0 97.9-78.0
46 Acetonitrile: Ether B 2.1-22.0 97.9-78.0 55.7 730.7
47 HCFC-225 ca/cb: Ether A 60.8-90.3  39.2-9.7 
48 HCFC-225 ca/cb: Ether B 60.8-90.3  39.2-9.7  53.1 738.3
*End point is an estimated value. Estimate assumes curve is symmetrical.

Examples 49 to 94 Preparation and Characterization of the Azeotrope-like Compositions by the Distillation Method

Mixtures of hydrofluorocarbon ether and one or more organic solvents which exhibited a boiling point depression in the Ebulliometer Method were evaluated again to more precisely determine the composition of the azeotrope. Mixtures of these hydrofluorocarbon and organic solvents were prepared and distilled in a concentric tube distillation column (Model 9333 from Ace Glass, Vineland, N.J.). The distillation was allowed to equilibrate at total reflux for at least 60 minutes. In each distillation, six successive distillate samples, each approximately 5 percent by volume of the total liquid charge, were taken while operating the column at a liquid reflux ratio of 20 to 1. The compositions of the distillate samples were then analyzed using an HP-5890 Series II Plus Gas Chromatograph (Hewlett-Packard) with a 30 m HP-5 capillary column (cross-linked 5% phenyl methyl silicone gum stationary phase), a 30m Stabilwax DA™ column (Alltech Assoc.) or a 30 m Carbograph I™ (Alltech Assoc.) and a flame ionization detector. The boiling points of the distillate were measured using a thermocouple which was accurate to about 1° C. The compositional data, boiling points and ambient pressures at which the boiling points were measured are reported in Table 3.

In some cases, both Ether A and Ether B were used to prepare azeotropes with the same organic solvent. For each such case, the standard deviation and mean of the concentrations of the azeotrope components were calculated and analyzed using a t-test (95% confidence level) to determine whether the differences in the azeotrope compositions prepared with Ether A and Ether B were statistically significant, or should be considered to be from the same population. Where the t-test indicated that the compositions were from the same population, the mean and standard deviation were calculated for the entire population (i.e., for Ether A and Ether B azeotropes) and the mean value is also reported.

The azeotropes were also tested for flammability by placing a small aliquot of the azeotrope in an open aluminum dish and holding a flame source in contact with the vapor of the azeotrope above the dish. Flame propagation across the vapor indicated that the azeotrope was flammable. The flammability data is presented in Table 3 under the heading “Flamability”. The flash points of select compositions were determined using a method similar to that described in ASTM D3278-89 test method B. Instead of cooling specimens using the aluminum cooling block described in test method B, specimens were cooled using solid CO2. The results of the evaluation are presented in Table 3 under the heading “Flash Point”.

TABLE 3
Organic
Ether Solvent Boiling Ambient
Organic Solvent: Conc. Conc. Point Pressure Flash
Ex. Ether (wt %) (wt %) (° C.) (torr) Flammability Point
49 Cyclohexane: Ether 88.0   12 ± 54 737.5 Yes
A 3.6
50 Methylcycloexane: 95.9  4.1 ± 58 734.4 No None
Ether A 0.9
51 Methylcyclohexane: 96.9  3.1 ± 59 737.5 No None
Ether B 0.3
52 Hexane: Ether A 78.9 21.1 ± 51 730.5 Yes
1.5
53 Heptane: Ether A 95.2  4.8 ± 57 724.8 No None
0.9
54 Heptane: Ether B 94.4  5.6 ± 59 729.4 Yes
0.3
55 Isooctane: Ether A 96.1  3.9 ± 58 724.8 No None
1.2
56 Isooctane: Ether B 96.3  3.7 ± 58 730.6 No None
0.9
57 Diisopropyl ether: 78.3 21.7 ± 56 730.5 Yes
Ether A 2.1
58 Methyl t-butyl 63.2 36.8 ± 51 738.2 Yes
ether: Ether A 3.3
59 Tetrahydrofuran: 79.4 20.6 ± 55 738.2 Yes
Ether A 1.8
60 Acetone: Ether A 65.0 35.0 ± 51 736.2 Yes
1.5
61 trans-1,2- 44.1 55.9 ± 40 732.9 No None
Dichloroethylene: 12.3
Ether A
62 trans-1,2- 50.3 49.7 ± 40 729.3 No None
Dichloroethylene: 1.2
Ether B
63 cis-1,2- 65.7 34.3 ± 50 741.2 No None
Dichloroethylene: 0.6
Ether B
64 1,1,2- 86.8 13.2 ± 58 743.5 No None
Trichloroethylene: 0.6
Ether B
65 1-Chlorobutane: 86.4 13.6 ± 56 738.0 Yes
Ether A 1.5
66 1-Chlorobutane: 87.8 12.2 ± 56 734.2 Yes
Ether B 1.5
67 2-Chlorobutane: 79.3 20.7 ± 56 740.6 Yes
Ether B 0.3
68 i-Butyl chloride: 80.0 20.0 ± 55 741.2 Yes
Ether B 0.1
69 t-Butyl chloride: 46.2 53.8 ± 47 732.6 Yes
Ether A 0.6
70 t-Butyl chloride: 47.3 52.7 ± 47 729.3 Yes
Ether B 0.6
71 1,2- 95.0  5.0 ± 58 734.4 No None
Dichloropropane: 0.6
Ether A
72 1,2- 94.5  5.5 ± 59 744.7 No None
Dichloropropane: 0.3
Ether B
73 2,2- 77.2 22.8   55 735.6 No None
Dichloropropane:
Ether A
74 2,2- 81.2 18.8 ± 55 727.4 No None
Dichloropropane: 0.3
Ether B
75 Methylene 44.9 55.1 ± 35 743.3 No None
Chloride: Ether B 0.6
76 Methanol: Ether A 96.3  3.7 ± 45 738.6 No None
0.9
77 Methanol: Ether B 89.6 10.4 ± 45 729.4 Yes
1.2
78 Ethanol: Ether A 97.0  3.0 ± 51 726.0 No None
0.3
79 Ethanol: Ether B 93.4  6.6 ± 53 740.0 Yes
0.6
80 2-Propanol: Ether A 96.8  3.2 ± 54 723.3 No None
0.6
81 2-Propanol: Ether B 93.3  6.7 ± 54 730.6 No None
0.9
82 1-Propanol: Ether A 98.4  1.6 ± 56 738.9 No None
0.1
83 1-Propanol: Ether B 97.4  2.6 ± 58 739.8 No None
0.3
84 2-Butanol: Ether B 98.0  2.0 ± 60 728.6 No None
0.6
85 i-Butanol: Ether B 98.8  1.2 ± 60 728.6 No None
0.3
86 t-Butanol: Ether B 93.8  6.2 ± 58 743.2 No None
0.1
87 Trifluoroethanol: 85.6 14.4 ± 40 738.3 No None
Ether B 0.6
88 Pentafluoropropanol: 88.6 11.4 ± 42 738.3 No None
Ether B 0.3
89 Hexafluoro-2- 57.5 42.5 ± 54 741.8 No None
propanol: Ether B 0.6
90 1-Bromopropane: 74.2 25.8 ± 54 730.8 No None
Ether B 0.1
91 Acetonitrile: Ether 92.0  8.0 ± 57 732.9 No None
A 0.3
92 Acetonitriie: Ether 93.3  6.7 ± 57 742.9 No None
B 0.1
93 HCFC-225ca/cb: 26.4 73.6   53 735.6 No None
Ether A
94 HCFC-225ca/cb: 30.6 69.4 ± 53 734.2 No None
Ether B 4.2

Examples 95-140

A number of the azeotropes were tested for their ability to dissolve hydrocarbons of increasing molecular weight according to the procedure described in U.S. Pat. No. 5,275,669 (Van Der Puy et al.) The data presented in Table 4 was obtained by determining the largest normal hydrocarbon alkane which was soluble in a particular azeotrope at a level of 50 volume percent. The hydrocarbon solubilities in the azeotropes were measured at both room temperature and the boiling points of the azeotropes. The data is reported in Table 4. The numbers in Table 4 under the headings “Hydrocarbon @ RT” and “Hydrocarbon @ BP” correspond to the number of carbon atoms in the largest hydrocarbon n-alkane that was soluble in each of the azeotropes at room temperature and at the boiling point of the azeotrope, respectively.

Azeotropes were prepared and their boiling points were measured using a resistance temperature detector. These measurements were accurate within about 0.2° C. and are presented in Table 4.

The data in Table 4 shows that hydrocarbon alkanes are very soluble in the azeotrope-like compositions of this invention, and so the azeotrope-like compositions are excellent solvents for the cleaning process of this invention. These compositions will also be effective as solvents for depositing hydrocarbon coatings, e.g., coatings of lubricant, onto substrate surfaces.

TABLE 4
Organic Hydrocarbon Hydrocarbon Boiling
Ether Solvent @ RT @ BP Point Ambient
Organic Solvent: Conc. Conc. (# carbon (# carbon Azeotrope Pressure
Ex. Ether (wt %) (wt %) atoms) atoms) (° C.) (torr)
 95 Cyclohexane: Ether 88.0 12.0 ± 10 13 54.6 725.6
A 3.6
 96 Methylcyclo- 95.9  4.1 ± 9 12 58.7 728.8
hexane: Ether A 0.9
 97 Methylcyclohexane: 96.9  3.1 ± 9 12 58.5 743.1
Ether B 0.3
 98 Rexane: Ether A 78.9 21.1 ± 11 15 52.2 729.1
1.5
 99 Heptane: Ether A 95.2  4.8 ± 10 12 58.8 733.2
0.9
100 Heptane: Ether B 94.4  5.6 ± 10 13 58.5 731.9
0.3
101 Isooctane: Ether A 96.1  3.9 ± 13 59.4 734.2
1.2
102 Isooctane: Ether B 96.3  3.7 ± 10 12 58.6 732.0
0.9
103 Diisopropyl ether: 78.3 21.7 ± 12 18 57.4 736.0
Ether A 2.1
140 Methyl t-butyl 63.2 36.8 ± 19 >24 51.6 728.8
ether: Ether A 3.3
105 Tetrahydrofuran: 79.4 20.6 ± 14 >17 55.6 729.4
Ether A 1.8
106 Acetone: Ether A 65.0 35.0 ± 14 18 50.7 735.6
1.5
107 trans-1,2- 44.1 55.9 ± 18 19 40.9 729.9
Dichloroethylene: 12.3 
Ether A
108 trans-1,2- 50.3 49.7 ± 16 19 40.8 739.5
Dichloroethylene: 1.2
Ether B
109 cis-1,2- 65.7 34.3 ± 14 19 54.9 740.6
Dichloroethylene: 0.6
Ether B
110 1,1,2- 86.8 13.2 + 10 14 57.9 743.5
Trichloroethylene: 0.6
Ether B
111 1-Chlorobutane: 86.4 13.6 ± 11 14 57.1 730.1
Ether A 1.5
112 1-Chlorobutane: 87.8 12.2 ± 11 14 56.7 731.5
Ether B 1.5
113 2-Chlorobutane: 79.3 20.7 ± 12 16 55.1 740.3
Ether B 0.3
114 i-Butyl chloride: 80.0 20.0 ± 12 15 54.9 740.7
Ether B 0.1
115 t-Butyl chloride: 46.2 53.8 ± 20 >24 47.2 722.6
Ether A 0.6
116 t-Butyl chloride: 47.3 52.7 ± 20 >24 47.6 743.2
Ether B 0.6
117 1,2- 95.0  5.0 ± 10 13 59.2 731.5
Dichloropropane: 0.6
Ether A
118 1,2- 94.5  5.5 ± 10 13 58.9 744.7
Dichloropropane: 0.3
Ether B
119 2,2- 77.2 22.8   12 16 55.9 723.0
Dichloropropane:
Ether A
120 2,2- 81.2 18.8 ± 12 15 55.4 727.4
Dichloropropane: 0.3
Ether B
121 Methylene chloride: 44.9 55.1 + 19 24 34.7 743.3
Ether B 0.6
122 Methanol: Ether A 96.3  3.7 ± 10 11 46.5 734.9
0.9
123 Methanol: Ether B 89.6 10.4 ± 10 11 45.8 732.9
1.2
124 Ethanol: Ether A 97.0  3.0 ± 10 12 52.6 735.6
0.3
125 Ethanol: Ether B 93.4  6.6 ± 10 13 52.0 732.5
0.6
126 2-Propanol: Ether A 96.8  3.2 ± 10 12 55.5 735.8
0.6
127 2-Propanol: Ether B 93.0  7.0 ± 10 13 54.7 737.3
0.9
128 1-Propanol: Ether A 98.4  1.6 ± 10 12 57.4 734.8
0.3
129 1-Propanol: Ether B 97.4  2.6 ± 10 12 56.2 729.2
0.3
130 2-Butanol: Ether B 98.0  2.0 ± 10 12 58.1 741.6
0.6
131 i-Butanol: Ether B 98.8  1.2 ± 9 12 58.3 742.5
0.3
132 t-Butanol: Ether B 93.8  6.2 ± 10 13 55.8 741.2
0.1
133 Trifluoroethanol: 85.6 14.4 ± 8 10 52.5 740.4
Ether B 0.6
134 Pentafluoropropanol: 88.6 11.4 ± 8 11 56.6 740.2
Ether B 0.3
135 Hexafluoro-2- 57.5 42.5 ± 7 9 52.5 747.6
propanol: Ether B 0.6
136 Acetonitrile: Ether 92.0  8.0 ± 9 12 54.4 728.8
A 0.3
137 Acetonitrile: Ether 93.3  6.7 ± 9 13 55.7 740.5
B 0.1
138 HCFC-225ca/cb: 26.4 73.6   19 >24 53.1 723.3
Ether A
139 HCFC-225 ca/cb: 30.6 69.4 ± 19 >24 53.3 740.4
Ether B 4.2
140 1-Bromopropane: 74.2 25.8 ± 12 15 53.0 723.9
Ether B 0.1

Examples 141-151

The following examples describe the preparation of azeotropes containing Ether B and two organic solvents.

Azeotrope composition was determined using the distillation method described in Examples 49-94, their boiling points were measured using the procedure described in Examples 95-140 and their cleaning power was determined using the procedure described in Examples 95-140. The data is presented in Table 5.

Azeotrope-like compositions containing within about 10 wt. % of each component contained in the azeotropes of Table 5 are useful azeotrope-like compositions in accordance with the invention and have many utilities such as cleaning solvents, coating composition solvents and drying agents.

TABLE 5
Hydrocarbon Hydrocarbon
Boiling @ RT @ BP
Weight Point Pressure (#carbon (# carbon Flamma-
Ex. Component (%) (° C.) (torr) atoms) atoms) bility
141 Ether B 51.9 36.3 732.2 15 18 Yes
1,2-t- 43.0 ±
Dichloro- 2.4
ethylene
Methanol  5.1 ±
2.4
142 Ether B 52.7 39.6 731.2 15 18 No
1,2-t- 44.6 ±
Dichloro- 2.4
ethylene
Ethanol  2.7 ±
0.6
143 Ether B 51.1 40.5 732.9 15 18 No
1,2-t- 48.6 ±
Dichloro- 2.7
ethylene
1-Propanol  0.3 ±
0.9
144 Ether B 51.7 40.5 736.7 15 18 No
1,2-t- 47.0 ±
Dichloro- 2.4
ethylene
2-Propanol  1.3 ±
0.6
145 Ether B 53.5 40.3 729.5 15 19 No
1,2-t- 45.9 ±
Dichloro- 11.7 
ethylene
t-Butanol  0.6 ±
0.6
146 Ether B 43.8 38.9 734.1 9 12 No
1,2-t- 46.8 ±
Dichloro- 0.3
ethylene
Trifluoro-  9.4 ±
ethanol 0.3
147 Ether B 47.4 40.4 733.7 14 18 No
1,2-t- 46.8 ±
Dichioro- 1.5
ethylene
Pentafluoro-1-  5.8 ±
propanol 1.8
148 Ether B 36.3 39.2 735.2 11 15 No
t- 44.3 ±
Dichloro- 0.3
ethylene
Hexafluoro-2- 19.4 ±
propanol 11.7 
149 Ether B 51.6 40.3 728.2 15 19 No
1,2-t- 48.1  
Dichloro-
ethylene
Acetonitrile 0.3
150 Ether B 45.6 45.8 733.5 14 17 No
HCFC-225 48.6 ±
ca/cb 1.8
Methanol  6.6 ±
0.3
151 Ether B 42.5 51.0 735.0 16 21 No
HCFC-225 53.2 ±
ca/cb 1.2
Ethanol  4.3 ±
0.1

Example 152

The following examples illustrate the use of one of the azeotropic compositions of this invention as a solvent or extraction media.

A mineral oil filled polypropylene microporous membrane prepared according to the procedure described in Example 10 of U.S. Pat. No. 4,726,989 was cut into 1.5×3.0 cm strips and weighed.

The oil-laden strips were subsequently immersed in either about 30 mLs of Ether B or about 30 mLs of an azeotrope-like composition consisting of 50 wt. % of Ether B and 50 wt. % of trans-1,2-dichloroethylene. The samples were lightly agitated in their respective solvent or extraction media for about one minute and then withdrawn and air-dried. The samples were then weighed to determine the amount of oil removed by Ether B and the azeotrope-like composition containing Ether B. Ether B removed 0.026±0.006 g oil per g of membrane while the azeotrope-like composition removed 0.379±0.015 g oil per g of membrane. This data demonstrates that some of the azeotrope like compositions of this invention are more effective solvents or extraction media than the Ether B alone.

Example 153

This example shows that an azeotrope like composition of the invention can be used in commercial dry cleaning processes.

Into four, 30 mL glass screw cap vials were added the following:

(1) about 40 g of Ether B and 10 drops (0.24 g) of SECAPUR DRY-MASTER™ dry cleaning detergent (a cationic detergent available commercially from Buesing & Fasch GmbH & Co-Reinigungs-u. Veredelungstechnik of Oldenburg, Germany);

(2) about 40 g of Ether B and 10 drops (0.24 g) of SECAPUR PERFECT™ dry cleaning detergent (an anionic detergent also available commercially from Buesing & Fasch GmbH);

(3) 40 g of mixture of 50 wt. % Ether B and 50 wt. % of trans-1,2-dichloroethylene, and about 10 drops (0.24 g) of SECAPUR DRY-MASTER™ detergent; and

(4) 40 g of a mixture of 50 wt. % Ether B and 50 wt. % of trans-1,2-dichloroethylene, and about 10 drops (0.24 g) of SECAPUR PERFECT™ detergent.

The bottles were shaken by hand and visually evaluated to determine the solubility of the detergents in the ether or azeotrope-like composition. Ether B did not dissolve either detergent, while the azeotrope-like composition dissolved both detergents. The bottle containing the azeotrope-ike composition and the SECAPUR DRY-MASTER™ detergent was somewhat hazy with 10 drops of the detergent, but it did not readily separate into separate phases. However, 5 drops (0.12 g) of SECAPUR DRY-MASTER™ detergent was fully soluble in the azeotrope-like composition.

Solutions of the detergent/azeotrope-like compositions described above were evaluated as dry cleaning agents for white cotton fabric swatches stained with dirty motor oil. Dirty motor oil was poured on 1.5×1.5 cm cotton fabric swatches and the swatches were then placed under a 500 g weight for 3 hrs to ensure good penetration of the oil into the fabric. The stained swatches were then placed in containers containing the detergent/azeotrope-like compositions described above, and the containers were capped and shaken for about 2 minutes. The swatches were then removed and air-dried before visually comparing them to unstained swatches. Both of the detergent-containing compositions were observed to have completely removed the oil stain from the swatches.

Examples 154-156

In the following examples, the compositions of azeotropes formed by trans-1,2-dichloroethylene and hydrofluorocarbon ether having various relative proportions of perfluoro-n-butyl methyl ether and perfluoroisobutyl methyl ether were determined.

25 mL mixtures of trans-1,2-dichloroethylene and hydrofluorocarbon ether having the relative proportions of perfluoro-n-butyl methyl ether and perfluoroisobutyl methyl ether specified in Table 6 were prepared. Each of the mixtures was distilled using an Ace Glass 9333 concentric tube distillation column having 40 theoretical plates (stated). In each distillation, the column was allowed to equilibrate for one hour at total reflux. The reflux ratio was subsequently adjusted to 20 to 1 and thereafter, six, 1 mL samples of distillate were removed from the receiver. Each of the samples was analyzed via gas chromatography using a Hewlett Packard 5890 GC containing an HP-5 capillary column from Hewlett Packard to determine the relative concentrations of trans-1,2-dichloroethylene and hydrofluorocarbon ether in the azeotropes. The relative proportions of perfluoro-n-butyl methyl ether and perfluoroisobutyl methyl ether in the hydrofluorocarbon ether and the concentration of trans-1,2-dichloroethylene and hydrofluorocarbon ether in the azeotropes is presented in Table 6.

TABLE 6
Concentration of Concentration of
Perfluoro-n-Butyl Perfluoroisobutyl Concentration of
Methyl Ether in Methyl Ether in Trans-1,2- Concentration of
Hydrofluorocarbon Hydrofluorocarbon Dichloroethylene Hydrofluorocarbon
Ether Ether in Azeotrope Ether in Azeotrope
Ex. (wt. %) (wt. %) (wt. %) (wt. %)
154 95 5 55.9 44.1
155 62.5 37.5 51.5 48.5
156 30 70 49.7 50.3

The data shows that despite the variation in the concentration of branched and straight chain isomers in the hydrofluorocarbon ether, the composition of the azeotrope formed with trans-1,2-dichloroethylene is largely unchanged.

Examples 157-158

The following examples illustrate that the effect of hydrofluoro isomer concentration on the boiling point curves for azeotropic compositions of hydrofluorocarbon ether and trans-1,2-dichloroethylene.

Using the method described in Examples 3-48, graphs of boiling point (° C.) as a function of composition (volume %) were prepared for mixtures of Ether A and trans-1,2-dichloroethylene and Ether B and trans- 1,2-dichloroethylene. The curves are presented in FIG. 1.

The data shows that the curves are very similar despite the different concentrations of perfluoro-n-butyl methyl ether in Ether A and Ether B. The relatively constant boiling point compositions prepared with Ether A (represented by the flat portion of the boiling point curve) contain between about 16.2 and 75.4 weight percent Ether A while the relatively constant boiling point compositions prepared with Ether B contain about 17.4 to 75.4 weight percent Ether B. The boiling point of Ether A is 40.7° C. at 727.5 torr and the boiling point of Ether B is 40.3° C. at 729.3 torr.

Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2713593Dec 21, 1953Jul 19, 1955Minnesota Mining & MfgFluorocarbon acids and derivatives
US3394878Aug 25, 1965Jul 30, 1968Du PontAzeotropic compositions
US3900372Sep 16, 1974Aug 19, 1975Phillips Petroleum CoRecycle of acyl fluoride and electrochemical fluorination of esters
US3903012Feb 14, 1973Sep 2, 1975Du PontWater-displacement compositions containing fluorine compound and surfactant
US4726989Dec 11, 1986Feb 23, 1988Minnesota Mining And ManufacturingMicroporous materials incorporating a nucleating agent and methods for making same
US5023009Oct 3, 1990Jun 11, 1991E. I. Du Pont De Nemours And CompanyBinary azeotropic compositions of 1,1,1,2,3,3-hexafluoro-3-methoxypropane and 2,2,3,3,3-pentafluoropropanol-1
US5023010Jul 23, 1990Jun 11, 1991E. I. Du Pont De Nemours And CompanyBinary azeotropic compositions of 1,1,1,2,3,3-hexafluoro-3-methoxypropane with methanol or isopropanol or N-propanol
US5034424Jun 28, 1990Jul 23, 1991Bosch-Siemens Hausgerate GmbhRigid foam and process for producing the same
US5064560Oct 11, 1990Nov 12, 1991E. I. Du Pont De Nemours And CompanyTernary azeotropic compositions of 43-10mee (CF3 CHFCHFCH2 CF.sub.
US5091104Jun 26, 1991Feb 25, 1992Allied-Signal Inc.Azeotrope-like compositions of tertiary butyl 2,2,2-trifluoroethyl ether and perfluoromethylcyclohexane
US5098595Jul 23, 1990Mar 24, 1992E. I. Du Pont De Nemours And CompanyTernary azeotropic compositions of 1,1,1,2,3,3-hexafluoro-3-methoxypropane and cis-1,2-dichloroethylene with methanol or ethanol or isopropanol or n-propanol
US5125978Oct 30, 1991Jun 30, 1992Minnesota Mining And Manufacturing CompanyWater displacement composition and a method of use
US5137932Dec 5, 1990Aug 11, 1992Hoechst AktiengesellschaftProcess for producing foams
US5211873Jul 21, 1992May 18, 1993Minnesota Mining And Manufacturing CompanyFine-celled plastic foam containing fluorochemical blowing agent
US5264462Mar 1, 1993Nov 23, 1993Imperial Chemical Industries PlcPolymeric foams
US5273592Nov 1, 1991Dec 28, 1993Alliesignal Inc.Method of cleaning using partially fluorinated ethers having a tertiary structure
US5275669Aug 15, 1991Jan 4, 1994Alliedsignal Inc.Method of dissolving contaminants from substrates by using hydrofluorocarbon solvents having a portion which is fluorocarbon and the remaining portion is hydrocarbon
US5466877Mar 15, 1994Nov 14, 1995Minnesota Mining And Manufacturing CompanyProcess for converting perfluorinated esters to perfluorinated acyl fluorides and/or ketones
US5484546May 13, 1994Jan 16, 1996E. I. Du Pont De Nemours And CompanyRefrigerant compositions including an acylic fluoroether
US5672307Mar 8, 1996Sep 30, 1997E. I. Du Pont De Nemours And CompanyFlash spinning process
US5718293Dec 15, 1995Feb 17, 1998Minnesota Mining And Manufacturing CompanyFire extinguishing process and composition
US5756002 *May 10, 1996May 26, 1998Occidental Chemical CorporationCleaning solvents containing benzotrifluoride and fluorinated compounds
US5792277Jul 23, 1997Aug 11, 1998Albemarle CorporationN-propyl bromide based cleaning solvent and ionic residue removal process
US5814595May 15, 1996Sep 29, 1998Minnesota Mining And Manufacturing CompanyAzeotrope-like compositions and their use
US5827446Jan 15, 1997Oct 27, 1998E. I. Du Pont De Nemours And CompanyNonafluoromethoxybutane compositions
US5827812May 15, 1996Oct 27, 1998Minnesota Mining And Manufacturing CompanyAzeotrope-like compositions and their use
US5851436May 19, 1997Dec 22, 1998E. I. Du Pont De Nemours And CompanyNonafluoromethoxybutane compositions
US6008179Sep 21, 1998Dec 28, 19993M Innovative Properties CompanyAzeotrope-like compositions and their use
US6063748Aug 6, 1998May 16, 20003M Innovative Properties CompanyAzeotrope-like compositions and their use
CA2098057A1Jun 9, 1993Dec 11, 1993Wilfried BeckerIsopropanol-containing cleaning solutions having an elevated flash point
DE1294949BMay 17, 1966May 14, 1969Hoechst AgVerfahren zur Herstellung von Perfluoralkyl-alkyl-aethern
DE1302054BNov 25, 1966Feb 5, 1970Hoechst AgVerfahren zur Herstellung von Perfluoralkyl-alkyl-aethern
EP0450855A2Mar 27, 1991Oct 9, 1991Imperial Chemical Industries PlcSolvent cleaning of articles
FR2287432A1 Title not available
GB2274462A Title not available
JPH06293686A Title not available
JPH07159821A Title not available
JPH08259995A Title not available
JPH08333292A Title not available
WO1996022356A1Jan 11, 1996Jul 25, 1996Minnesota Mining & MfgCleaning process and composition
Non-Patent Citations
Reference
11995 American Chemical Society., Predictions of Azeotropes Formed From Fluorinated Ethers, Ethanes, and Propanes. Authors: Gage, C.L.; Kazachki, G. S. Report date: 1992.
2B.N. Ellis, Cleaning and Contamination of Electronics Components and Assemblies, Electrochemical Publications Limited, Ayr, Scotland, pp. 182-194, (1986).
3Cooper et al., Atmos. Environ. 26A, 7, 1331 (1992).
4Flynn et al., "Azeotrope-Like Compositions And Their Use", USSN 09/429,186, filed Oct. 28, 1999.
5Flynn et al., "Azeotrope-Like Compositions And Their Use", USSN 09/429,508, filed Oct. 28, 1999.
6Flynn et al., "Azeotrope-Like Compositions And Their Use", USSN 09/783,358, filed Feb. 14, 2001.
7Flynn et al., "Azeotrope-Like Compositions And Their Use", USSN 09/783,359, filed Feb. 14, 2001.
8Flynn et al., "Azeotrope-Like Compositions And Their Use", USSN 09/783,702, filed Feb. 14, 2001.
9H. Kobler et al., Justus Liebigs Ann. Chem., 1978, 1937.
10Intergovernmental Panel, Climate Change: The IPCC Scientific Assessment, Cambridge University Press (1990).
11M.C. Sneed and R.C. Brasted, Comprehensive Inorganic Chemistry, Volume Six (The Alkali Metals), pp. 61-64, D. Van Nostrand Company, Inc., New York 91957).
12P.S. Zurer, "Looming Ban on Production of CFCs, Halons Spurs Switch to Substitutes," Chemical & Engineering News, p. 12, Nov. 13, 1993.
13Preparation, Properties and Industrial Applications of Organofluorine Compounds, R. E. Banks, ed., John Wiley and Sons, New York, 1982, pp. 19-43.
14Y. Tang, Atmospheric Fate of Various Fluorocarbons, M.S. Thesis, Massachusetts Institute of Technology (1993).
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6699829Jun 7, 2002Mar 2, 2004Kyzen CorporationCleaning compositions containing dichloroethylene and six carbon alkoxy substituted perfluoro compounds
US7053036Oct 30, 2002May 30, 2006Poly Systems Usa, Inc.Compositions comprised of normal propyl bromide and 1,1,1,3,3-pentafluorobutane and uses thereof
US7288511Oct 29, 2003Oct 30, 2007Kyzen CorporationCleaning compositions containing dichloroethylene and six carbon alkoxy substituted perfluoro compounds
US7468142 *Nov 7, 2001Dec 23, 2008Solvay S.A.Solvent compositions
US8245512Mar 11, 2011Aug 21, 2012Solvay Fluor GmbhWorking fluid comprising a fluorinated ketone for an ORC process, and ORC apparatus
US8748363Nov 2, 2012Jun 10, 2014Du Pont-Mitsui Fluorochemicals Co., Ltd.Solvent composition for removing radioactive substance and removing material, and method for removing radioactive substance
US20100108094 *Jul 29, 2005May 6, 2010Junichi IshikawaSolvent Composition for Removing Radioactive Substance and Removing Material, and Method for Removing Radioactive Substance
Classifications
U.S. Classification510/411, 134/42, 252/364, 510/285, 252/67, 106/311
International ClassificationC11D7/28, C23G5/028, C11D7/50, C23G5/032
Cooperative ClassificationC11D7/5072, C23G5/032, C11D7/5063, C23G5/02806, C11D7/5086, C23G5/02851, C11D7/28, C23G5/028, C11D7/5077
European ClassificationC11D7/50D2M, C11D7/50D4B, C23G5/028D2C25, C23G5/032, C11D7/50D4D4, C23G5/028, C11D7/50D4D, C23G5/028C
Legal Events
DateCodeEventDescription
Mar 7, 2013FPAYFee payment
Year of fee payment: 12
May 6, 2009FPAYFee payment
Year of fee payment: 8
May 6, 2005FPAYFee payment
Year of fee payment: 4